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Semester 2
CHAPTER 1:
THERMOCHEMISTRY
1.1
Introduction
Energy is one of the most fundamental parts of our universe. We use
energy to do work. Energy lights our cities. Energy powers our vehicles,
trains, planes and rockets. Energy warms our homes, cooks our food,
plays our music, gives us pictures on television. Energy powers
machinery in factories and tractors on a farm.
According to the conservation of energy law, energy can be neither
created nor destroyed; it can only be converted from one form into
another
From the angle of chemistry, when a chemical reaction occur, energy
changes occur generally in 2 ways, where it can be explained in terms
of kinetic energy and energetic energy. In this chapter, we focus more
on the study of energy changes, in the form of heat, which take place
during a chemical reaction occur, which is well known as
thermochemistry.
In order to understand thermochemistry, we must first understand what
is the difference between system and surrounding. System is the
specific part of substances that involved in chemical and physical
change, while surrounding is defined as the rest of the universe
outside the system.
Closed system
Isolated system
We shall focus more on a closed system throughout our lesson, with the
assumption that energy lost by system in a chemical reaction is the
same with the energy gained by surrounding. In thermochemistry
energy that were gained / lost by system were measured by heat energy.
In the laboratory, heat changes in physical and chemical processes are
measured with a calorimeter, a closed container designed specifically for
this purpose. Our discussion of calorimetry, the measurement of heat
changes, will depend on an understanding of specific heat and heat
capacity,
The specific heat capacity (c) of a substance is the amount of heat
required to raise the temperature of one gram of the substance by one
degree Celsius. It has the units J g-1C-1.
The heat capacity (C) of a substance is the amount of heat required to
raise the temperature of a given quantity of the substance by one degree
Celsius. Its units are J C-1.
Specific heat is an intensive property whereas heat capacity is an
extensive property.
The relationship between the heat capacity and specific heat capacity
of a substance is
C = c x m (mass)
H = positive (+ve)
H = negative (ve)
Endothermic
exothermic
Process
Definition
Energy
profile
Endothermic
Process of heat
absorbed by system
Positive
Exothermic
Process of heat
released by system
Negative
Process
Endothermic
Exothermic
Temperature decrease
Temperature increase
3 STEPS ON CALCULATING
ENTHALPY CHANGE
1
q=mc
mass MV
mol =
or
MR
1000
H =
q
mol
Question 1 : Solution
Equation : Zn (s) + H2SO4 (aq) ZnSO4 (aq) + H2 (g)
Step 1 : q = m c @ q = (25.0) (4.18) (31.5 27.0)
q = 470.25 J
Question 2 : Solution
Equation : Na2SO4 + Ba(NO3)2 2 NaNO3 + BaSO4
Step 1 : q = m c
@ q = (20.0 + 30.0) (4.18) (34.0 30.0)
q = 836 J
Step 2 : determine limitant
mol Na2SO4 = MV /1000 mol Ba(NO3)2 = MV /1000
= (0.500) (20.0) / 1000
= (0.300) (30.0) / 1000
= 0.010 mol
= 0.0090 mol (lim)
Step 3 : H = q / mol @
H = 836 / 0.0090
H = 92889 J / mol 92.9 kJ / mol
Question 3 : Solution
Equation : 2 KI + Pb(NO3)2 2 KNO3 + PbI2
Step 1 : q = m c
@ q = (20 + 30) (4.18) (34 29)
q = 1045 J
Step 2 : determine limitant
mol KI = MV /1000
mol Pb(NO3)2 = MV /1000
= (0.18) (30) / 1000
= (0.15) (20) / 1000
= 0.0054 mol
= 0.0030 mol
Step 3 : H = q / mol @
H = 1045 / 0.0027 mol
H = 387037 @ = 390 kJ / mol
Question 4 : Solution
NaCl + AgNO3 NaNO3 + AgCl
Step 3 : From H and mol ; find q
Step 2 :
mol of AgNO3 = MV / 1000 mol of NaCl = MV / 1000
= (1.00)(10.0) / 1000
= (0.800)(15.0) / 1000
= 0.010 mol (lim)
= 0.012 mol
so
q = H x mol @ q = ( 63400) (0.010)
q = 634 J
Step 1 : q = m c @
= q / mc
= 634 / [(4.18) (10.0 + 15.0)
= 6.07 oC
Examples
CO2
NaCl
Hf more exothermic
Reaction between Na and X2 more vigorous
Stability of compound formed increase
Hrxn of a reaction can be calculated using Hf
Hrxn = Hf (products) Hf (reactants)
Example 5
Example 6
Hrxn
Examples
C : C (s) + O2 (g) CO2 (g) [= Hfof CO2]
H2 : H2 (g) + O2 (g) H2O (l) [= Hfof H2O]
C2H5COOH : C2H5COOH (l) + 7/2 O2 (g)
3 CO2 (g) + 3 H2O (l)
C2H5OH : C2H5OH (l) + 3 O2 (g) 2 CO2 (g) + 3 H2O (l)
Mg : Mg (s) + O2 (g) MgO (s)
P
: P4 (s) + 5 O2 (g) P4O10 (s)
Al : Al (s) + 3/4 O2 (g) Al2O3 (s)
C6H12O6 : C6H12O6 (s) + 6 O2 (g) 6 CO2 (g) + 6 H2O (l)
Advantages :
Simple
Disadvantages :
The
Example 7
Step 1 : q = m c
@ q = (150) (4.18) (71.0 27.8)
q = 27.1 kJ
Step 2 : calculate the mol of pentane burned
mol = mass / RMM = 4.30 / 72
= 0.0597 mol
Step 3 : H = q / mol @
H = 27.1 kJ / 0.0597 mol
H = 454 kJ / mol
Bomb Calorimeter
Heat capacity , C =
temperature change ( )
q = H x mol
C=q/
H =
q
mol
mol = mass
RMM
q=C
Example 10 :
H = 16.2 kJ
0.0123
=-1310 kJ/ mol
mol = 0.625
122
= 5.12 x 10-3mol
q = -3230 x 5.12 x
= 16.5 kJ
10-3
C =16.5 / 1.58
= 10.5 kJ / K
mol = 0.712
58
= 0.0123 mol
q = 10.5 x 1.54
= 16.2 kJ
B
HM
Z
HN
Energy / kJ
1/8 S8 (s) + 3/2 O2 (g)
Energy / kJ
N2H4 (g) + H2 (g)
N2 (g) + 3 H2 (g)
2 NH3 (g)
Example 9 :
Find H2 (g) + O2 (g) H2O2 (l)
H2 (g) + O2 (g) H2O (l)
Hf = - 286 kJ/mol
H2O2 (g) H2O (l) + O2 (g)
H = - 188 kJ/mol
Reverse equation (2) => equation (3)
H2O (l) + O2 (g) H2O2 (g) H = +188 kJ
(3)
H2 (g) + O2 (g) H2O (l) Hf = - 286 kJ/mol
(1)
So, when equation (1) + (3)
H2 (g) + O2 (g) H2O2 (l)
H = - 98 kJ/mol
(1)
(2)
Energy / kJ
H2 (s) + O2 (g)
H2O2 (l)
Example 10 :
From these data,
S(rhombic) + O2(g) SO2(g)
Hrxn = - 296.06 kJ/mol
S(monoclinic) + O2(g) SO2(g) Hrxn = - 296.36 kJ/mol
Calculate the enthalpy change for the transformation
S(rhombic) S(monoclinic)
Energy / kJ
sulphur (rhombic) + O2 (g)
sulphur (monoclinic) + O2 (g)
SO2 (g)
(l)
Hf = 125 kJ / mol
Energy / kJ
4 C (s) + 5 H2 (g) + 13/2 O2 (g)
C4H10 (l) + 13/2 O2 (g)
4 CO2 (g)
Example 11 :
Given Hc of C2H2 and C6H6 are 1300 kJ / mol and 3270
kJ/mol respectively. Find 3 C2H2 (g) C6H6 (l)
C2H2 (g) + 5/2 O2 (g) 2 CO2 (g) + H2O (l) Hc = 1300 (1)
C6H6 (l) + 15/2 O2(g) 6 CO2(g) + 3 H2O(l) Hc = 3270 (2)
Multiply equation (1) by 3
Reverse equation (2)
3C2H2 (g) + 15/2 O2 (g) 6 CO2 (g) + 3 H2O (l) Hc = 3900
6 CO2(g) + 3 H2O(l) C6H6 (l) + 15/2 O2 (g) Hc = +3270
3 C2H2 C6H6 (l)
H = 630 kJ
Energy / kJ
3 C2H2 (g) + 15 / 2 O2 (g)
C6H6 (l) + 15/2 O2 (g)
Example 12 :
C3H6 (g) + H2 (g) C3H8 (g)
H = 124 kJ/mol
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l) Hc = 2222 kJ/mol
H2 (g) + O2(g) H2O (l)
Hc = 286 kJ / mol
Find for C3H6(g) + 9/2 O2(g) 3 CO2(g) + 3 H2O(l) Hc = ?
Reverse equation (3)
H2O (l) H2 (g) + O2(g)
Hc = + 286 kJ / mol
C3H6 (g) + H2 (g) C3H8 (g)
H = 124 kJ/mol
C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l) Hc = 2222 kJ/mol
C3H6(g) + 9/2 O2(g)3 CO2(g) + 3 H2O(l) Hc= 2060 kJ/mol
Energy / kJ
C3H6 (g) + H2 (g) + 5 O2 (g)
C3H8 (g) + 5 O2 (g)
C3H6 (g)
1.6
Enthalpy change of Neutralisation H neut
~ amount of energy liberated when 1 mol of hydrogen ion from
acid react with 1 mol of hydroxide ion from alkali to form 1
mole of water under standard condition.
Equation : H+ (aq) + OH (aq) H2O (l)
Hneut for strong acid and strong base under standard
condition is 57.3 kJ / mol.
The value of Hneut will be different with weak acid / base is
used or if the acid used is a polyproctic acid
In laboratory, Hneut can be determine using simple cup
calorimeter (MPM Experiment 6)
The ways of calculating Hneut is still the same as we
learned previously.
Example
Equation : HCl (aq) + NH3 (aq) NH4Cl (aq)
Step 1 : q = m c @ q = (25.0 + 30.0) (4.18) (31.3 27.6)
q = 850.63 J
Step 2 : determine limitant
mol of HCl = MV / 1000
= (1.00)(25.0)/1000
= 0.025 mol
the
Reaction involving HF :
HF (aq) + NaOH (aq) NaF (aq) + H2O (l)
Hneut= 102.4 kJ / mol
The reaction become more exothermic than expected
despite that HF is consider as a weak acid. When HF is
dissolve in water, H-F dissociate in water to form H+ and F-.
The enthalpy of hydration, Hhyd of the fluoride ion is very
exothermic, making the overall process to be much
exothermic
F- (g) + water F- (aq)
Hhyd = 63.4 kJ/mol
1.6
Standard Enthalpy Change of Atomisation, Hatom
~ energy absorbed when 1 mole of gaseous atoms are formed
from its element under standard condition.
Eq : A (s) A (g)
Hatom = + ve kJ/mol
Example :
Mg (s) Mg (g)
P4 (s) P (g)
Cl2 (g) Cl (g)
Na (s) Na (l)
Na (l) Na (g)
Na (s) Na (g)
Hfusion
Hvapourisation
Hatom
1.7
Ionisation energy, HIE
~ energy absorbed when 1 mole of electron is removed from a
gaseous atom under standard condition.
Eq : A (g) A+ (g) + eHIE = + ve kJ/mol
The process is always endothermic as heat is absorbed to
free one mole of electron from an atom (to overcome the
electrostatic forces of attraction between the nucleus and
outermost electron)
Generally, when goes down to Group, ionisation energy
decrease, while across the Period, ionisation energy
increase. These trend shall be further discussed in Chapter 3
It is believed that, when enormous amount of energies is
supplied, electrons in an atom can be removed completely
from an atom. The energies required to consecutively
remove the electrons from an atom is called as successive
ionisation energies
1.8
Electron Affinity HEA
~ energy liberated when 1 mole of electron is received from gaseous
atom under standard condition.
Eq : O (g) + e- O (g)
HEA = X kJ / mol
For 1st Electron Affinity, the process is always exothermic, since
upon receive an electron, the energy carries by the electron is
released upon combining with the gaseous atom.
The trend of of 1st electron affinity is the same as in Ionisation
energy, where 1st electron affinity decrease when going down
to group, whereas the 1st electron affinity increase when going
across Period.
However, unlike 2nd ionisation energy, after an atom received an
electron an form negative charged ion, upon receiving the second
electron, a repulsion forces is felt between the anion and electron
receive, due to the mutual charge between both substance.
Hence, for second electron affinity, heat is absorbed
(endothermic) by the anion to overcome the repulsion forces
between the anion and electron.
1.9
Lattice Energy, HLE
~ energy liberated when 1 mole of solid crystal lattice is
formed from oppositely charged gaseous ions under
standard condition.
Eq : M+ (g) + X (g) MX (s)
HLE = X kJ/mol
LE always negative (exothermic) : heat is released when
ionic bond is formed.
Examples of writing thermochemical equation :
Lattice energy
Z n+ Z n
r+ + r
Compound
Total
charge
Ionic
radius
Compound
Total
charge
Ionic
radius
NaF
0.231
NaCl
0.276
KBr
0.328
KCl
0.314
CaO
0.239
MgO
0.205
Al2O3
0.190
K2O
0.273
KBr < KCl < NaCl < NaF < K2O < CaO < MgO < Al2O3
Lattice energy increase
Hatom of Cl
HIE of Na
HLEof NaCl
NaCl (s)
Hf = HLE + [Hatom Na + Hatom Cl + H1st IE Na + H1st EA Cl]
HLE = (-411) [(+108) + (+121) + (+494) + (-364)]
= 770 kJ/mol
2 x HEA of Cl
HLEof CaCl2
CaCl2 (s)
Hf = HLE + [Hatom Ca + 2Hatom Cl + H1st IE Ca +
H2nd IE Ca + 2H1st EA Cl]
HLE = (-795) [(+132) + 2(+121) +(+590) +(1150) + 2(-364)]
= 2181 kJ/mol
HLEof K2O
2 K (g) + O2 (g)
2 X Hatom of K
2 K (s) + O2 (g)
Hf of K2O
K2O (s)
Hf = HLE + [2Hatom K + HBE O + 2H1st IE K +
H1st EA O + H2nd EA O]
HLEof MgO
Mg (g) + O2 (g)
Hatom of Mg
Mg (s) + O2 (g)
Hf of MgO
MgO (s)
Hf = HLE + [Hatom Mg + HBE O +H1st IE Mg +
H2nd IEMg + H1st EA O + H2nd EA O]
HLE = (-612) [(+146) + (+498)+(736) + (1450) + (-141)+(+844)]
= 3896 kJ/mol
HLEof Cr2O3
Cr2O3 (s)
HLE = 16408 kJ/mol
water.
\\\\\\\\\\\\\\\\\...under
standard condition.
n+ (g) + water Mn+ (aq)
M
Hhyd = x kJ/mol
Equation :
Mn+
Qn-
Group 2 sulphate
Be SO4
Mg SO4
Ca SO4
Sr SO4
Ba SO4
-95.3
-91.2
+ 17.8
+ 18.70
+19.4
Solubility
(g / 100mL)
41.0
36.4
0.21
0.010
0.00025
Hhydration
Hlattice energy
BeSO4
Mg SO4
CaSO4
Sr SO4
BaSO4
Sr2+
Ba2+
Be2+
Ca2+
Mg2+
SO42-